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  • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
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  • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
  • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
  • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
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Definitions

• the present invention relates to a process for hydrocyanation of ethylenically unsaturated organic compounds into compounds comprising at least one nitrile function.
• It relates more particularly to the hydrocyanation of diolefins such as butadiene or of substituted olefins such as alkenes nitrites such as pentenenitriles.
• diolefins such as butadiene or of substituted olefins such as alkenes nitrites such as pentenenitriles.
• the hydrocyanation of butadiene into pentenenitriles is an important reaction which has been implemented industrially for many years, in particular in the process for the synthesis of adiponitrile, a large chemical intermediate allowing in particular access to the monomers of many polymers, including mainly polyamides.
• French Patent No. 1,599,761 describes a process for the preparation of nitriles by adding hydrocyanic acid to organic compounds having at least one ethylenic double bond, in the presence of a nickel catalyst and a triaryl phosphite. This reaction can be carried out in the presence or not of a solvent.
• a solvent is preferably a hydrocarbon, such as benzene or xylenes or a nitrile such as acetonitrile.
• the catalyst used is an organometallic nickel complex, containing ligands such as phosphines, arsines, stibines, antimonites, arsenites, phosphites, phosphinites or phosphonites.
• ligands such as phosphines, arsines, stibines, antimonites, arsenites, phosphites, phosphinites or phosphonites.
• the processes for hydrocyanating dienes generally comprise two stages: a first hydrocyanation leading to branched and linear unsaturated mononitriles and a second stage making it possible to obtain the dinitriles.
• a first hydrocyanation leading to branched and linear unsaturated mononitriles and a second stage making it possible to obtain the dinitriles.
• linear nitriles are of interest for the synthesis of new products such as adiponitrile for example.
• These methods therefore also include an intermediate step called isomerization step, consisting in treating the branched unsaturated mononitriles to transform them into linear unsaturated mononitriles.
• Patent FR-A-2,338,253 has proposed carrying out the hydrocyanation of compounds having at least one ethylenic unsaturation, in the presence of an aqueous solution of a compound of a transition metal, in particular nickel, palladium or iron, and a sulfonated phosphine.
• the sulfonated phosphines described in this patent are sulfonated triarylphosphines and more particularly sulfonated triphenylphosphines. This process allows a correct hydrocyanation, in particular of butadiene and pentenenitriles, an easy separation of the catalytic solution by simple decantation and by Consequently, as much as possible avoids the discharge of effluents or waste containing the metals used as catalyst.
• One of the aims of the present invention is to propose a new family of ligands which makes it possible to obtain, with the transition metals, catalytic systems having in particular an improved selectivity in linear nitriles compared to known systems.
• the present invention provides a process for hydrocyanation of a hydrocarbon compound comprising at least one ethylenic unsaturation by reaction in a liquid medium with hydrogen cyanide in the presence of a catalyst comprising a metallic element chosen from the metals of transition and an organic ligand characterized in that the organic ligand corresponds to the following general formula I:
• T identical or different represent a phosphorus, arsenic or antimony atom
• Ri, R 2> R3, 4 identical or different represent an aromatic, aliphatic or cycloaliphatic radical, substituted or not, comprising one or more rings in condensed form or not and which can comprise one or more heteroatoms, the radicals Ri, and R 2 of a on the other hand, R 3 and R 4 on the other hand can be linked together by a covalent bond, a hydrocarbon chain or a heteroatom;
• Ui, U 2 , U 3 , U 4 identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical,
• L ,, L 2 when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR 7 , PR 8 , SiR 9 R 10l BRu, S, POR ⁇ 2 , SO 2 , CO, -CR ⁇ 4 R ⁇ 5 -, in which R 7 has the meaning of R indicated above, R 8 and R 12 may represent the radical OR 3 , and R 8 , Rg, Rio, Rn, ⁇ 2 , ⁇ 3 , R ⁇ and R ⁇ 5 represent alkyl, aryl or cycloalkyl radicals, R ⁇ 4 and R ⁇ 5 can also represent the hydrogen atom.
• R ⁇ 7 represent an alkyl, aryl, halogen, aikoxy, thiol, cyano, nitro, aryloxy, aikoxycarbonyl, acyl, formyl radical.
• the catalyst advantageously corresponds to the general formula (II):
• M is a transition metal
• L f represents the organic ligand of formula (I)
• t represents a number between 1 and 4 (limits included)
• the metals which can be complexed with the organic ligands of the invention are generally all the transition metals of groups 1b, 2b, 3b, 4b, 5b, 6b, 7b and 8 of the periodic table of the elements, as published in "Handbook of Chemistry and
• metals there may be mentioned more particularly the metals that may be mentioned by way of nonlimiting examples, nickel, cobalt, iron, ruthenium, rhodium, palladium, osmium, iridium, platinum , copper, silver, gold, zinc, cadmium, mercury.
• the preparation of organometallic complexes comprising the organic ligands of the invention can be carried out by bringing a solution of a compound of the chosen metal into contact with a solution of the organic ligand of the invention.
• the metal compound can be dissolved in a solvent.
• the metal can be found in the compound used, either at the degree of oxidation that it will have in the organometallic complex, or at a higher degree of oxidation.
• rhodium is at the degree of oxidation (I), ruthenium at the degree of oxidation (II), platinum at the degree of oxidation (0), palladium at the oxidation state (0), osmium at the oxidation state (II), iridium at the oxidation state (I), cobalt at the oxidation state (I), nickel at the oxidation state (0).
• the metal is used at a higher degree of oxidation, it can be reduced in situ.
• organometallic complexes comprising the organic ligands of the invention can be used as catalysts in the hydrocyanation reactions of olefins.
• the compounds of the transition metals are preferably used.
• the most preferred compounds are those of nickel.
• - nickel compounds such as carboxylates (especially acetate), carbonate, bicarbonate, borate, bromide, chloride, citrate, thiocyanate, cyanide, formate, hydroxide, hydrophosphite, phosphite, phosphate and derivatives, iodide, nitrate, sulfate, sulfite , aryl- and alkylsulfonates.
• a reducing agent for nickel reacting preferentially with the latter under the reaction conditions is added to the reaction medium.
• This reducing agent can be organic or mineral.
• borohydrides such as Bh ⁇ Na, BH4K, Zn powder, magnesium or hydrogen may be cited.
• the nickel compound used corresponds to the oxidation state of nickel, it is also possible to add a reducing agent of the type of those mentioned above, but this addition is not imperative.
• the reducing agents can also be elements of the reaction medium (phosphine, solvent, olefin).
• the organic compounds comprising at least one ethylenic double bond more particularly used in the present process are the diolefins such as butadiene, isoprene, hexadiene-1,5, cyclooctadiene-1,5, the aliphatic nitriles with unsaturation ethylenic, in particular linear pentenenitriles such as pentene-3-nitrile, pentene-4-nitrile, monoolefins such as styrene, methylstyrene, vinyinaphthalene, cyclohexene, methylcyclohexene as well as mixtures of several of these compounds.
• diolefins such as butadiene, isoprene, hexadiene-1,5, cyclooctadiene-1,5, the aliphatic nitriles with unsaturation ethylenic, in particular linear pentenenitriles such as pentene-3-nit
• Pentenenitriles in particular may contain amounts, generally in the minority, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, l adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating for example from the previous hydrocyanation reaction of butadiene to unsaturated nitriles.
• other compounds such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, l adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, originating for example from the previous hydrocyanation reaction of butadiene to unsaturated nitriles.
• the catalytic system used for hydrocyanation according to the process of the invention can be prepared before its introduction into the reaction zone, for example by adding to the ligand according to the invention alone or dissolved in a solvent, the appropriate amount of compound of the transition metal chosen and optionally of the reducing agent. It is also possible to prepare the catalytic system "in situ" by simple addition of the ligand and of the transition metal compound in the hydrocyanation reaction medium before or after the addition of the compound to be hydrocyanated.
• the amount of nickel compound or of another transition metal used is chosen to obtain a concentration in mole of transition metal per mole of organic compounds to be hydrocyanated or isomerized between 10 "4 and 1, and preferably between 0.005 and 0.5 mole of nickel or of the other transition metal used.
• the amount of organic ligands of the invention used to form the catalyst is chosen such that the number of moles of this compound, based on 1 mole of transition metal, is from 0.5 to 50 and preferably from 1 to 10.
• the solvent can be a catalyst solvent which is miscible in the phase comprising the compound to be hydrocyanated at the hydrocyanation temperature.
• solvents that may be mentioned are aromatic, aliphatic or cycloaliphatic hydrocarbons.
• This solvent can also be partially miscible with the compounds to be hydrocyanated, in particular when the reaction medium is at a temperature below the reaction temperature. Thus, it is possible, at such temperatures, to obtain a two-phase system. In the case where the catalytic system is soluble in said solvent, its extraction from the reaction medium is facilitated.
• Such partially miscible or immiscible solvents can be water or molten organic salts of an ionic nature.
• Such solvents are used in particular when the organic ligand comprises anionic radicals making it soluble in ionic media.
• These radicals are, for example, sulfonate, carbonate, carboxylate, phosphate, ammonium, guanidinium, imidazolium groups, substituting the aromatic radicals of the ligand.
• the hydrocyanation reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably from 30 ° C to 120 ° C. It is advantageously carried out in a single-phase medium, at the reaction temperature.
• the method of the invention can be implemented continuously or discontinuously.
• the hydrogen cyanide used can be prepared from metallic cyanides, in particular sodium cyanide, or cyanhydrins, such as acetone cyanohydrin or by any other known synthesis process.
• the hydrogen cyanide is introduced into the reactor in gaseous, gas mixture or liquid form. It can also be previously dissolved in an organic solvent. In the context of a discontinuous implementation, it is in practice possible to charge into a reactor, previously purged using an inert gas (such as nitrogen, argon), either a solution containing all or part of the various constituents such as the organic ligand of the invention, the transition metal compound, any reducing agents and solvents, or separately said constituents. Generally the reactor is then brought to the chosen temperature, then the compound to be hydrocyanated is introduced. The hydrogen cyanide is then itself introduced, preferably continuously and regularly.
• an inert gas such as nitrogen, argon
• reaction mixture is withdrawn after cooling and the products of the reaction are isolated, for example, by distillation.
• An improvement to the process for hydrocyanation of ethylenically unsaturated compounds according to the present invention relates in particular to the hydrocyanation of said ethylenically unsaturated nitrile compounds, by reaction with hydrogen cyanide and consists in using a catalytic system in accordance with the present invention with a cocatalyst consisting of at least one Lewis acid.
• the ethylenically unsaturated compounds which can be used in this improvement are generally those which have been mentioned for the basic process.
• pentenenitriles may contain quantities, generally in the minority, of other compounds, such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, resulting from the previous hydrocyanation reaction of butadiene and / or from the isomerization of methyl-2-butene-3-nitrile into pentenenitriles.
• other compounds such as methyl-2-butene-3-nitrile, methyl-2-butene-2-nitrile, pentene-2-nitrile, valeronitrile, adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or butadiene, resulting from the previous hydrocyanation reaction of butadiene and / or from the isomerization of methyl-2
• the Lewis acid used as cocatalyst allows in particular, in the case of the hydrocyanation of aliphatic nitriles with ethylenic unsaturation, to improve the linearity of the dinitriles obtained, that is to say the percentage of linear dinitriles relative to the all of the dinitriles formed, and / or of increasing the activity and the lifetime of the catalyst.
• Lewis acid is meant in the present text, according to the usual definition, compounds that accept electronic doublets.
• the Lewis acids which can be used as cocatalysts in the present process are chosen from the compounds of the elements of groups Ib, llb, Nia, lllb, IVa, IVb, Va, Vb, Vlb, Vllb and VIII of the periodic table elements.
• These compounds are generally salts, in particular halides, such as chlorides or bromides, sulfates, sulfonates, halogénoalkyisulfonates, perhalogénoalkyisulfonates including fluoroalkylsulfonates or perfluoroalkylsulfonates, the halogénoalkylacmony oxidees, the perhalogénoalkylacmony oxidees including fluoroalkylacuitees or perfluoroalkylacetat.es, carboxylates and phosphates.
• halides such as chlorides or bromides
• Lewis acids there may be mentioned zinc chloride, zinc bromide, zinc iodide, manganese chloride, manganese bromide, cadmium chloride, bromide cadmium, stannous chloride, stannous bromide, stannous sulfate, stannous tartrate, indium trifluoromethylsulfonate, indium trifluoroacetate, zinc trifluoroacetate, chlorides or bromides of rare earth elements such as lanthanum, cerium , praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, hafnium, Perbium, thallium, ytterbium and lutetium, cobalt chloride, ferrous chloride, chloride yttrium.
• rare earth elements such as lanthanum, cerium , praseodymium, neodymium, samarium, europium, ga
• Organometallic compounds such as triphenylborane or titanium isopropylate can also be used as the Lewis acid. It is of course possible to use mixtures of several Lewis acids.
• Lewis acids zinc chloride, zinc bromide, stannous chloride, stannous bromide, triphenylborane and zinc chloride / stannous chloride mixtures, indium trifluoromethylsulfonate and indium trifluoroacetate are particularly preferred. , zinc trifluoroacetate.
• the Lewis acid cocatalyst used generally represents from 0.01 to 50 moles per mole of transition metal compound, more particularly of nickel compound, and preferably from 0.5 to 10 moles per mole.
• the catalytic solution used for hydrocyanation in the presence of Lewis acid can be prepared before its introduction into the reaction zone, for example by adding to the reaction medium the ligand of formula (I), of the appropriate quantity of compound of the transition metal chosen, of Lewis acid and optionally of the reducing agent. It is also possible to prepare the catalytic solution "in situ" by simple mixing of these various constituents.
• methyl-2-butene-3-nitrile in admixture with methyl-2-butene-2 nitrile, pentene-4-nitrile, pentene-3-nitrile, pentene-2-nitrile, butadiene , adiponitrile, methyl-2-glutaronitrile, ethyl-2-succinonitrile or valeronitrile.
• the isomerization reaction is generally carried out at a temperature of 10 ° C to 200 ° C and preferably from 60 ° C to 160 ° C.
• the catalytic system used for isomerization can be prepared before its introduction into the reaction zone, for example by adding the ligand of formula (I), the amount compound of the chosen transition metal and optionally the reducing agent. It is also possible to prepare the catalytic system "in situ" by simple addition of these various constituents in the reaction medium.
• the amount of transition metal compound and more particularly of nickel used, as well as the amount of ligand of formula (I) are the same as for the hydrocyanation reaction.
• the isomerization reaction is generally carried out without solvent, it may be advantageous to add an inert organic solvent which may be that of the subsequent extraction. This is particularly the case when such a solvent has been used in the hydrocyanation reaction of the butadiene which served to prepare the medium subjected to the isomerization reaction.
• solvents can be chosen from those which have been mentioned above for hydrocyanation.
• the preparation of dinitrile compounds by hydrocyanation of an olefin such as butadiene can be carried out using a catalytic system in accordance with the invention for the stages of formation of the unsaturated mononitriles and the stage of isomerization above, the reaction of hydrocyanation of mononitriles unsaturated with dinitriles which can be used with a catalytic system according to the invention or any other catalytic system already known for this reaction.
• the hydrocyanation reaction of the olefin to unsaturated mononitriles and the isomerization of these can be carried out with a catalytic system different from that of the invention, the step of hydrocyanation of the mononitriles unsaturated to dinitriles being carried out. works with a catalytic system according to the invention.
• organophosphorus compounds corresponding to the following general formula I:
• T Ti identical or different represent an atom of phosphorus, arsenic or antimony
• R 3 , R 4 which may be identical or different, represent an aromatic, aliphatic or cycloaliphatic radical, substituted or not, comprising one or more rings in condensed form or not and possibly comprising one or more heteroatoms, the radicals R 1; and R 2 on the one hand, R 3 and R 4 on the other hand can be linked together by a covalent bond, a hydrocarbon chain or a heteroatom;
• U 1 , U 2 , U 3 , U 4 identical or different, represent an oxygen atom or a radical of formula NR in which R denotes a monovalent alkyl, aryl, cycloalkyl, sulfonyl or carbonyl radical,
• L when n is equal to 0, represents a divalent radical chosen from the group comprising the groups NR 7 , PR 8 , SiR 9 R 10 , BRu, S, POR 12 , SO 2 , CO in which R 7 has the meaning of R indicated above, R 8 and R 12 may represent the radical OR 13; and R 8 , Rg, RIQ, RU R ⁇ 2 and R 13 represent alkyl, aryl or cycloalkyl radicals; L ⁇ , L 2 when n is equal to 1, identical or different represent a covalent bond, a radical chosen from the group comprising the groups O, NR 7 , PR 8 , SiR 9 R 10 , BR- ⁇ , S, POR ⁇ 2 , SO 2 , CO, -CR ⁇ 4 Ri5-, in which R 7 has the meaning of R indicated above, R 8 and R 12 may represent the radical OR 13 , and R 8 , R 9 , R 10 , Ru, R ⁇ 2 , R ⁇ 3 , R ⁇ 4 and R 15 represent alkyl
• 4PN 4-pentenenitrile. 3 + 4PN: 3PN + 4PN.
• TT (Y) transformation rate of the product to be hydrocyanated Y corresponding to the ratio of the number of transformed moles of Y to the number of initial moles of Y.
• CPG gas chromatography. ml: milliliter. mol: mole. mmol: millimole.
• Procedure 1 A phosphochloridite prepared from a phenol or biphenol derivative and from PCI 3 is used according to a conventional procedure (see for example the method described by G. Buisman et Al. In Tetrahedron, Asymmetry, vol 4 , (7), pp 1625-1634 (1993)), and a commercially available diol. The following general procedure is representative:
• a phosphoramidite prepared from CI 2 PNEt 2 (commercially available) and a substituted or unsubstituted phenol is used according to the following procedure:
• the suspension is kept under vigorous stirring for 18 h at 25 ° C., then filtered under argon on a bed of basic alumina. After rinsing with toluene, the filtrate is concentrated under reduced pressure to yield the desired product, used without further purification.

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